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CN105171985A - Large area nanopatterning method and apparatus - Google Patents

Large area nanopatterning method and apparatus Download PDF

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Publication number
CN105171985A
CN105171985A CN201510644135.6A CN201510644135A CN105171985A CN 105171985 A CN105171985 A CN 105171985A CN 201510644135 A CN201510644135 A CN 201510644135A CN 105171985 A CN105171985 A CN 105171985A
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CN
China
Prior art keywords
mask
radiation
cylinder
substrate
nano
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CN201510644135.6A
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Chinese (zh)
Inventor
B·柯宾
I·兰道
B·沃尔夫
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Metamaterial Technologies USA Inc
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Rolith Inc
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Publication of CN105171985A publication Critical patent/CN105171985A/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C33/00—Moulds or cores; Details thereof or accessories therefor
    • B29C33/42—Moulds or cores; Details thereof or accessories therefor characterised by the shape of the moulding surface, e.g. ribs or grooves
    • B29C33/424—Moulding surfaces provided with means for marking or patterning
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
    • G03F1/62—Pellicles, e.g. pellicle assemblies, e.g. having membrane on support frame; Preparation thereof
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
    • G03F1/50—Mask blanks not covered by G03F1/20 - G03F1/34; Preparation thereof
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
    • G03F1/60—Substrates
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
    • G03F7/2014—Contact or film exposure of light sensitive plates such as lithographic plates or circuit boards, e.g. in a vacuum frame
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G03F7/24—Curved surfaces
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
    • H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
    • H01L21/0274—Photolithographic processes

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Shaping Of Tube Ends By Bending Or Straightening (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
  • Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)

Abstract

Embodiments of the invention relate to methods and apparatus useful in the nanopatterning of large area substrates, where a rotatable mask is used to image a radiation- sensitive material. Typically the rotatable mask comprises a cylinder. The nanopatterning technique makes use of Near-Field photolithography, where the mask used to pattern the substrate is in dynamic contact with the substrate. The Near-Field photolithography may make use of an elastomeric phase-shifting mask, or may employ surface plasmon technology, where a rotating cylinder surface comprises metal nano holes or nanoparticles.

Description

Large area nanopatterning method and equipment
The application is international filing date is on November 18th, 2008, and entering thenational phase day is the divisional application that the name on July 9th, 2010 is called the Chinese patent application 200880124519.3 of " large area nanopatterning method and equipment ".
Technical field
Embodiments of the invention relate to and can be used for by large-sized substrate or substrate, such as, can be used as the nanopatterning method of the film patterning of rolling commodity selling.Other embodiments of the invention relate to the equipment that can be used to tpo substrate patterning, and this equipment can be used to manner of execution embodiment, comprising the embodiment of the method described.
Background technology
This section describes the background theme relating to disclosed embodiment of the present invention.Intention, does not represent or implies that the background technology described in this joint forms the intention of prior art legally.
Nano-structured (nanostructuring) is required to many present application and industry, and is required to the new technology developed.Such as and not as restriction, can be the current application in such as solar cell and LED field, and the current application in further generation data storage device realize the improvement in effect.
Nano-structured substrate can use following fabrication techniques, such as electron-beam direct writing (e-beamdirectwriting), deep-UV lithography (DeepUVlithography), nanosphere lithography (nanospherelithography), nano-imprint lithography (nanoimprintlithography), near field phase-shift photolithography (near-fieldphaseshiftlithography), and such as plasma photoetching (plasmoniclithography).
Nano-imprint lithography (NIL), by the mechanically deform of impression resist (imprintresist), succeeded by subsequent technique, creates pattern.Impression resist normally during impressing by heat or by the monomer (monomeric) of UV photocuring or condensate (polymeric) formulation.NIL has many changes.But two kinds in technique seemingly most important.These techniques are thermoplasticity (Thermoplastic) nano-imprint lithography (TNIL) and stepping and flash of light (stepandflash) nano-imprint lithography (SFIL).
TNIL is the earliest and the most ripe nano-imprint lithography.In standard TNIL technique, the thin layer spin coated of impression resist (thermoplastic polymer) is in sample substrate.Then will have mould and the sample contacts of predefined topological pattern, and extrude sample at a given pressure.When being heated to above the temperature of amorphous phase-change (glasstransition) temperature of thermoplastic polymer, the pattern press-in thermoplastic polymer film melt on mould.After the sample cooling with impressing mould, mould from sample separation, and impresses resist and stays on sample substrate surface.Pattern is not through impression resist; The residual thickness of unchanged thermoplastic polymer film is had to remain on sample substrate surface.Pattern transfering process, such as reactive ion etching (reactiveionetching), can be used for the design transfer in resist to underlying substrate.Change in the residual thickness of unaltered thermoplastic polymer film proposes problem, this problem relate to for by design transfer to the uniformity of the etch process of substrate and optimization.
In SFIL technique, curable UV liquid resist is applied to sample substrate, and mould is by transparent substrates, and such as vitreous silica is made.Mould and sample substrate pinched together after, use UV photocuring resist, and resist becomes solid.After mould is separated from the anticorrosive additive material of solidification, the pattern similar to the pattern used in TNIL can be used to design transfer to lower floor's sample substrate.All there is many challenges in SFIL and TNIL technique, comprise model life-span, throughput, embossed layer tolerance during by design transfer to underlying substrate, and critical dimension controls.Residue non-embossed layer remaining after imprint process needs the additional etching steps before master pattern transfer etching.Owing to keeping the problem of uniform pressure over a large area, single game NIL has difficulty in the uniformity controlling the pattern copied on high surface area substrate.Step-and-repeat method can hide large area potentially, but the micro-structural formed in each step is independent of other step, and does not form seamless micro-structural over a large area when not splicing or nanostructured is problem.Stitching error occurs when the incorrect adjustment of the design transfer repeated.
If can obtain the roller surface of uniform pattern, so volume to volume (roll-to-roll) technique is possible.The uncensored patent of Japan is open, No.59200419A, be disclosed on November 13rd, 1984, its title is " LargeAreaExposureApparatus ", in this patent is open, the people such as ToshioAoki describe the use of transparent cylindrical cylinder (cylindricaldrum), and this rotatingcylindrical drum can rotate and translation together with patterning photomask (photomask) material membrane be attached to outside this rotatingcylindrical drum with internal light source.Transparent heat-reflecting material film is present in cylinder.There is aluminium film in its surface contact with the patterning photomask on cylinder surface with the substrate of photoresist (photoresist) of aluminium coating film, and imaging is through photomask, thus makes photoresist imaging on aluminium film surface.Photoresist develops subsequently (developed), thus provides patterned photo glue.Then patterned photo glue is as the etching mask of the aluminium film be present on substrate.
Do not relate to as photomask film, or be used as the description of material category of photoresist on aluminium film surface.High-pressure sodium lamp light source (500W) is used for the photoresist imaging of aluminium coating film.Use rotatingcylindrical drum design transfer equipment, produce and be approximately 210mm (8.3 inches) × 150mm (5.9 inches), and thickness is approximately the glass substrate of 0.2mm (0.008 inch).The characteristic size of the pattern of this technique transfers is used to be approximately 500 μm 2, be that there is the square being approximately 22.2 μm × 22.2 μm of sizes in appearance.This characteristic size is based on the approximate pixel size of this patent application light-emitting diode display when submitting to for 1984.Photomask film outside rotatingcylindrical drum it is said and continues nearly 140,000 design transfer.The contact lithograph scheme used by people such as ToshioAoki can not produce sub-micron features.
Disclose the information of (custombuilt) laboratory scale volume to volume coining tool about customization the people such as TapioMakela of the Technical Research Center VTT of Finland, this instrument is for the manufacture of the submicrometer structure with high-throughput.Hitachi and other development of company NIL prototype of sheet material or volume to volume, and illustrate the ability of the long sheet material of process 15 meters.Object uses belt moulding (nickel molds) to create continuous embossed technique, thus be the application of large-scale geometry, and the barrier film (membranes) of such as fuel cell, battery and possible display impress polystyrene sheet material.This prototype tool does not supply the handling capacity of requirement at present.In addition, need to improve the reliability about stamping surface and repeatability.Toshiba also discloses the information about the volume to volume UV coining tool allegedly producing submicron feature sizes.
The nano imprint lithography comprising volume to volume NIL still must overcome many challenges.Defect can be produced by the shrinkage phenomenon being not exclusively full of and often occurring about polymeric material of negative pattern.Between mould and substrate, the difference of thermal coefficient of expansion causes lateral strain, and this strain concentrates on the corner of pattern.During demoulding step, this strain causes defect in the foundation of pattern and causes fracture defect.In addition, the non-uniform thickness of remaining after imprint process residue non-embossed layer is harmful especially for the uniform etching pattern in the extensive substrate obtained below impression resist layer.
Soft lithographic is the alternate embodiment of the photoetching as micron and nanometer preparation method.This technology relates to the duplicating molded of self-assembled monolayer (monolayers).In soft lithographic, the elastomeric stamp (stamp) in its surface with patterning embossment structure is used for the pattern of generating feature size in 30nm to 100nm scope and structure.Most promising soft lithography is the micro-contact printing (μ CP) with self-assembled monolayer (SAMS).The basic technology of μ CP comprises: 1. dimethione (polydimethylsiloxane) mould is immersed special material liquid, wherein special material can form self-assembled monolayer (SAM).Such special material can be described as ink.Outstanding pattern is pasted onto on PDMS first type surface by this special material.2. there is the surface of the PDMS mould of ventricumbent material coated surfaces and the substrate of metal coat, the surface contact of substrate of such as gold or silver coating, the substrate of the pattern contacts metal coat therefore only on PDMS die surface.3. special material forms the chemical bond with metal, and the special material therefore only on outstanding patterned surfaces still remains on the surface of metal coat after PDMS mould removes.Special material forms SAM on the substrate of metal coat, and the substrate of this metal coat extends nearly one to two nanometers (ink just as on a piece of paper) in the surface of metal coat.4.PDMS mould removes from the surface of the metal coat of substrate, and the surface of metal coat stays patterning SAM.
(best-established) special material that the surface of gold or silver coating forms the determination of SAM best is alkyl sulfide alkoxide (alkanethiolate).Terminal hydroxy groups (Hydroxyl-terminatedmoieties) is contained, such as Si/SiO at substrate surface 2, Al/Al 2o 3, glass, mica, and during the polymer of plasma treatment (plasma-treated), alkylsiloxane (alkysiloxanes) is respond well as special material.About alkyl sulfide alkoxide, the μ CP seemingly the most reproducible technique of the hexadecyl mercaptan (hexadecanethiol) on gold or silver-colored evaporation thin (10-200nm is thick) film.Although these perform the foremost material that pattern formed, gold and silver with incompatible based on the microelectronic device of silicon technology, although can use containing gold or silver-colored electrode or wire.At present, at Si/SiO 2the μ CP of the SAMS of the siloxanes (siloxanes) on surface the equally easy processing of SAMS of the alkyl sulfide alkoxide of discord on gold or silver.At Si/SiO 2on the SAMS of siloxanes chaotic SAM is often provided, and generate subband structures (submonolayers) or multilayer in some cases.Finally, the useful pattern mould of μ CP is smooth " seal " surface, and over a large area renewable and printing reliably not only need point-device splicing of the printed patterns being derived from mould, also need the seal constant moisture with the special material forming SAM, this is very problematic.
Some new near field optic photoetching techniques based on the effect that suddenly dies (evanescenteffect) show advantage in the sub-100nm structure of printing, although just on small size.Near field phase-shift photolithography NFPSL comprises photoresist layer is exposed to ultraviolet (UV) light, this ultraviolet light when elasticity phase mask and photoresist bringing into conformal contact (conformalcontact) through this mask.Elasticity phase mask is contacted with photoresist thin layer and causes resist " to get wet " surface of contact surface of mask.When mask contacts with photoresist, this photoresist is made to be exposed to the light intensity distributions of developing in mask surface through this mask UV light.When mask has through designing with the relief depth of π adjustment transmitted light phase place, the local null value in intensity appears at the step edge of embossment.When using positive photoresist, by making such mask exposure, succeeded by development, produce the lines of the width photoresist equal with the characteristic width of null value in intensity.For 365nm (near ultraviolet) light in conjunction with conventional lithographic glue, in intensity, the width of null value is close to 100nm.PDMS mask can be used to be formed the contact with the conformal atomic scale of the smooth solid layer of photoresist.This contact is sent out and is set up on contact, does not have applying pressure.General adhesion guides this technique, and provides simply and the easily method at the angle of calibration mask on the direction perpendicular to photoresist surface and position, thus sets up perfect contact.Not about the physical-gap of photoresist.PDMS is greater than the UV optical transparency of 300nm to wavelength.When PDMS and photoresist layer bringing into conformal contact, photoresist is made to be exposed to the intensity distribution formed at mask from mercury lamp (wherein main spectral line is 355-365nm) through PDMS light.
On the 32nd the international microns of 2006 and nanometer engineering meeting, YasuhisaInao is describe by Canon in the report of " Near-FieldLithographyasaprototypenano-fabricationtool " at title, stepping and the photoetching of repetition near-field nanometer of Inc. development.Near field photolithography (NFL) is used, and wherein the distance that shifts between mask and photoresist of pattern is near as much as possible.Initial distance between mask and wafer substrate is set as about 50 μm.Patterning techniques is described to use " three layers of resist technique " of very thin photoresist.Design transfer mask is attached to pressure vessel bottom and supercharging, thus realizes " perfect physical contact " between mask and crystal column surface.This mask " is deformed thus is suitable for this wafer ".50 μm of distances initial between mask and wafer it is said and allow mask to move to another position, to make the area exposure and the patterning that are greater than 5mm × 5mm.Patterning system utilizes i line (i-line) (365nm) radiation be derived from as the mercury lamp of light source.The successful patterning with 4 inches of Silicon Wafers of the structure being less than 50nm is realized by such stepping and repetition methods.
Be in the document of " Large-areapatteringof50nmstructuresonflexiblesubstratesu singnear-field193nmradiation " at title, JVSTB21 (2002), at 78-81 page, the people such as Kunz use hard vitreous silica mask and dark UV wavelength exposure, by near field phase-shift mask lithography application in the nano-patterning of flexible sheet material (polyimide film).Be in the document subsequently of " Experimentalandcomputationalstudiesofphaseshiftlithograp hywithbinaryelastomericmasks " at title, JVSTB24 (2) (2006), at 828-835 page, the people such as Maria propose use with the experience of the phase shifting lithography of two elasticity phase masks of photoresist layer bringing into conformal contact with the research calculated.This work combines the mask optimized, and this mask passes through prepolymer, casts and be cured as to be attached to SiO 2the elastomer poly-(dimethyl siloxane (dimethylsiloxane)) of the anisotropic etching structure of the monocrystalline silicon on/Si is formed.Authors report use PDMS phase mask, thus the ability forming resist feature in whole geometries of sculpture on mask.
The US patent number No.6 of the people such as Rogers, 753,131, be disclosed on June 22nd, 2004, its title is " TransparentElastomeric, Contact-ModePhotolithographyMask; Sensor; andWavefrontEngineeringElement ", that patent describes the photoetching phase mask of contact mode, and this photoetching phase mask comprises the Difraction surface with multiple depression and protrusion.By this protrusion and positive photoresist surface contact, and this surface is exposed to the electromagnetic radiation through phase-shift mask.Owing to passing and protruding the radiation of contrary depression, phase shift completes substantially.Therefore the boundary of the minimum of electromagnetic radiation intensity between depression and protrusion produces.Flexible mask meets photoresist surface well, and along with the development of photoresist, can obtain the feature being less than 100nm.(summary) in one embodiment, reflecting plate substrate with contact mask outside use, so radiation is reflected to the requirement position in phase shift.In another embodiment, substrate can be shaped by the mode causing phase-shift mask to be out of shape, and this distortion affects the characteristic of phase-shift mask between exposure period.
The U.S. Patent Application Publication No.U.S.2006/0286488 of the people such as Rogers, be disclosed on December 21st, 2006, its title is " MethodsAndDevicesForFabricatingThree-DimensionalNanoscal eStructures ", the publication describes the method making 3-D structure on the surface of a substrate.This 3-D structure can use applicable elasticity phase mask to generate, and this elasticity phase mask can with the radiation-sensitive materials bringing into conformal contact standing optical treatment (thus producing this 3-D structure).This 3D structure can not penetrating radiation sensitive material completely.(summary)
Near-field surface plasma photoetching (NFSPL) utilizes near field to excite to cause photochemistry or optical physics change, thus produces nanostructured.Main near field technique is based on when irradiating metal Nano structure with surface plasma body resonant vibration frequency, and the local field around metal Nano structure strengthens.Plasma printing is made up of the use of plasma, and the use of this plasma guides evanescent wave by metal Nano structure, thus produces photochemistry and optical physics change in layer below metal structure.Especially, visible exposure (λ=410nm) close to the silver nano-grain of g Lithography glue film (being derived from the AZElectronicMaterials of German Ulm, the AZ-1813 of MicroChemicalsGmbH) can produce the region having selection exposure that diameter is less than λ/20.The people such as W.Srituravanich are in the document of " PlasmonicNanolithography " at title, NanolettersV4, N6 (2004), describing at 1085-1088 page uses nearly UV light (λ=230nm ~ 250nm) to excite SP on the metallic substrate, thus strengthens transmission by sub-wavelength period aperture wavelength effectively shorter compared with incentive optical wavelength.In Wei UV district, the plasma mask of lithography design is made up of the aluminium lamination and two insulating barriers surrounding aluminium lamination being carved with 2 dimension non-periodic pore battle arrays, and there is an insulating barrier the every side of aluminium lamination.Because aluminium can excite SP in UV district, so select aluminium.Quartz is used as mask and supports substrate, and this mask support substrate has poly-(methyl methacrylate) separate layer serving as aluminium flake adhesive and the insulator between aluminium and quartz.Because poly-(methyl methacrylate) and quartz are transparency and the comparable dielectric constant (quartz and PMMA are respectively 2.18 and 2.30) of the UV light of exposure wavelength (wavelength is the i line of 365nm) for wavelength, poly-(methyl methacrylate) combines quartzy use.Sub-100nm (sub-100nm) lattice array pattern on the 170nm cycle uses the exposing radiation of wavelength 365nm successfully to generate.The entire area of obvious pattern is approximately 5 μm × 5 μm, does not have the scalability problem discussed in paper.
It seems method for stamping (heat cure or UV solidification) or use the soft lithographic with the printing of SAM material not to be high manufacturability technique.Usually, shrink due to heat treatment (such as hot NIL) or about the pattern characteristics (polymer features of UV solidification) of condensate solidification, method for stamping creates the distortion of backing material.In addition, due to applying pressure (firmly contacting) between seal and substrate, defect is substantially inevitable, and the seal life-span is very limited.Soft lithographic does not have hot stamping brush and without the advantage in pressure printing technology.But, due to the drift of molecule from the teeth outwards, so it is very problematic for sub-100nm patterning that SAM is used as " ink ", and SAM is used as " ink " and applies over a large area and also do not prove experimentally.
Summary of the invention
Embodiments of the invention relate to about 200mm 2to about 1,000,000mm 2method and apparatus useful in the nano-patterning of the extensive substrate in scope, this scope is only example and not conduct restriction.In some instances, substrate can be have the good film of the sale of given width and undefined length.Nano-patterning technology utilizes near field UV photoetching, is wherein used for the mask of tpo substrate patterning and substrate dynamic Contact, or the substrate that closely (in evanscent field, is less than 100nm).Near field photolithography can comprise phase-shift mask or surface plasma body technique.Use the obtainable feature size range of method described to be down to about 1nm from about 1 μm, and scope is often be down to about 10nm from about 100nm.
An embodiment of exposure sources comprises phase-shift mask, and the form of this phase-shift mask is have the transparent rotatable mask of the UV of special phase shift embossment on the outer surface.In another embodiment of phase-shift mask technology, it is the polymer film of phase-shift mask that normally cylindrical transparent rotatable mask can have, and this mask is attached on this cylindrical outer surface.Contact uniformly with the excellent of substrate surface being difficult to obtain, during especially large processing area, polymer film is become to be produced by Van-derWaals power and the conformal elastomeric polymer film of outstanding bringing into conformal contact of substrate, such as PMDS is favourable.Polymer film phase-shift mask can be made up of multiple layer, and its ectomesoderm by nano-patterning, thus shows the characteristic size specified in radiosensitive (photosensitive) layer more accurately.
Another embodiment of exposure sources adopts soft elastic optical mask material, such as PDMS film, and this soft elastic optical mask material has a upper nontransparent feature made in its surface, and this surface is attached on cylindrical outer surface.Such feature can be use a kind of chromium feature produced on PDMS film in photoetching technique known in the art.
In the embodiment of exposure sources comprising surface plasma body technique, metal level or rete merging are deposited on the outer surface of the rotatable mask of normally transparent cylinder.Metal level or film have a series of special nanometer through hole.In another embodiment of surface plasma body technique, metal nano-particle layer is deposited on the outer surface of transparent rotatable mask, thus realizes the patterning of surface plasma enhancing.Radiation source provides in transparent cylinder inside.Such as and not as restriction, UV lamp can be arranged on cylinder inside.In alternative embodiments, radiation source can be placed on outside cylinder, and the light being derived from radiation source is transported to cylinder inside by cylindrical one or both ends.Use comprises such as speculum, lens or its optical system combined can focus on the specific region in cylinder by the radiation be derived from outside cylinder or in cylinder.Use grating the radiation be present in cylinder can be focused on mask substrate contact area.Radiation can be focused on mask substrate region (coupling) by the waveguide (waveguide) with grating.Waveguide or grating are placed in cylinder usually, thus radiation are heavily focused on the contact area between cylindrical outer surface and substrate surface be imaged.
In the particularization embodiment of the light source of radiation, flexible OLED display can be additional around rotatable mask outside, thus each luminous towards substrate from pixel.In this example embodiment, rotatable mask needs not be transparent.In addition, the light sent by control OLED, the special pattern transferring to the radiation-sensitive materials on substrate surface can generate according to application.The pattern be transferred " being in operation " can change when not needing to close production line.
Make substrate or rotatable mask, such as cylinder moves relative to one another, and contributes to the high-throughput providing design transfer to radiation-sensitive materials, and improves the quality of nano-patterning surf zone.At substrate static or substrate towards cylinder move and cylinder is static time, cylinder rotates on the surface of a substrate.According to the reason discussed below, it is favourable for being moved towards cylinder by substrate.
The amount that can control the power that the contact wire (being such as present in the contact wire between the elastic nano patterned film on periphery and the photoresist on substrate surface) between cylinder on the surface of a substrate and radiation-sensitive materials occurs is important.This cylinder by tensioning apparatus, such as, can compensate the spring supporting of cylinder weight, thus controls this contact wire.Substrate or cylinder (or both are whole) move (up or down) towards the other side mutually, therefore the interval between surface is reduced, contact is produced until periphery and radiation-sensitive materials between (such as, elastic nano patterned film on the surface of a substrate and photoresist).Elastic nano patterned film makes every effort to achieve the connection of building and having photoresist through Van-derWaals.Then substrate position (downwards) retracts the position of spring elongates, but elastic nano patterned film keeps in touch photoresist.Then substrate can move towards cylinder, forces cylinder to rotate, and keeps the dynamic Contact between elastic nano patterned film on the surface of a substrate and photoresist.Alternatively, the rotatable and substrate of cylinder can independently movement, but in synchronizing moving, and the rotatable and substrate of cylinder can independently move guarantees that free slippage (slip-free) contacts during dynamic exposure.
Multiple cylinder can be incorporated in a system, and the sensitive surface of substrate is exposed with sequential modes through arrangement, thus provides the dual, triple of substrate surface, and multigraph patterning.This exposure technique can be used to provide more high-resolution.Cylinder region of interest can be controlled by interferometer (interferometer) and suitable computerization control system.
In another embodiment, exposure dose can affect photoetching, therefore edge photoetching (such as, wherein can form narrow feature, this feature meets the movement of phase place in PDMS mask) can be changed into Conventional contact photoetching, and the characteristic size in the photoresist of imaging is by exposure dose control.By controlling power of radiation source or cylinder rotating speed (time for exposure), it is possible for controlling exposure dose like this.The characteristic size produced in the photoresist also by Change Example as the wavelength of exposing radiation, light source controls.
Mask on the cylinder can orientation angled with substrate moving direction.This makes pattern can be formed on the different directions contrary with substrate.Two or more cylinder can be placed in the sequence, thus 2D is patterned to as possibility.
In another embodiment, transparent column room needs not to be hard, but the flexible material that can be pressurizeed by available optical transparent gas is formed.Mask can be cylindrical wall can be maybe be present in the conformable material on cylindrical wall surface.This allows cylinder rolling on uneven substrate with during substrate surface bringing into conformal contact.
Accompanying drawing explanation
Therefore according to the special description that provides above, and according to providing the one exemplary embodiment of diagrammatic view, the detailed description of applicant, the method obtaining one exemplary embodiment of the present invention in method is clear and definite and can understands in detail.People will appreciate that, view only provides when one exemplary embodiment of the present invention understood by needs, and some famous technology and equipment is not in this diagram, in order to avoid the invention character of theme of the present disclosure is obscure.
Figure 1A illustrates the profile of an embodiment of equipment 100 useful in backing material large area pattern, and wherein radioparent cylinder 106 has the inside 104 of hollow, and radiation source 102 is present in this inside 104.In this embodiment, the outer surface 111 of cylinder 106 is by special surface embossment 112 patterning.Cylinder 106 rolls on the radiation-sensitive materials 108 covering substrate 110.
Figure 1B illustrates the top view of graphic equipment and substrate in Figure 1A, and wherein radiation-sensitive materials 108 has been through the radiation (not shown) imaging 109 of surface relief 112.
Fig. 2 illustrates the profile of another embodiment of equipment 200 useful in backing material large area pattern.In fig. 2, substrate is film 208, and when film 208 moves to volume 213 from volume 211, the pattern on this film 208 is passed in the radiant image of the surface relief 212 on first (transparent) cylinder 206.Second cylinder 215 provides on the back 209 of film 208, thus the contact between controlling diaphragm 208 and the first cylinder 206.
Fig. 3 illustrates the profile of another embodiment of equipment 300 useful in backing material large area pattern.In figure 3, substrate is the film 308 moving to volume 313 from volume 311.First transparent cylinder 306 with surface relief 312 is used for top 310 patterning of film 308, and second transparent cylinder 326 with surface relief 332 is used for bottom 309 patterning of film 308.
Fig. 4 A illustrates the profile of the embodiment 400 of the transparent cylinder 406 comprising the hollow area 404 with internal source of radiation 402.Surface relief region 412 is the conformal structures comprising the polymer film 415 with useful especially patterned surface 413 near field photolithography.
Fig. 4 B illustrates the amplification on surface 413, and this surface 413 is the surface relief polymer architectures 413 on polymer-based material 415.In figure 4b, polymer-based material 415 can be the polymeric material identical with patterned surface material 413, can be maybe the polymeric material different from patterned surface material 413.
Fig. 5 A illustrates the profile of the alternative embodiment 500 of the surface relief 512 be present on the transparent cylinder 506 of hollow.
Fig. 5 B illustrates the amplification of surface relief 512, and this surface relief 512 is the thin metal layers 514 by a series of nano-pore 513 patterning, and wherein this metal level is applied on the outer surface 511 of the transparent cylinder 506 of hollow.
Fig. 5 C illustrate can be used on transparent cylinder 506 surface on replaceable surface relief 522.Surface relief 522 is formed by metallic particles 526, and this metallic particles 526 can directly be applied on the outer surface 511 of the transparent cylinder 506 of hollow, or can be applicable on the hyaline membrane 524 of outer surface 511 of the transparent cylinder 506 being attached to hollow.
Fig. 6 A is the schematic three dimensional views 600 of the transparent cylinder 604 with patterned surface 608, is wherein used as spring graphic tensioning apparatus 602 to be suspended on above substrate 610 by cylinder 604.
Fig. 6 B is the schematic diagram of embodiment 620, and the radiation being wherein used for being embodied as picture is supplied from the radiation source 612 in cylinder 604 outside, and radiation is inner distribution 615 and 616 inside the hollow space of cylinder 604.
Fig. 6 C is the schematic diagram of embodiment 630, and the radiation being wherein used for being embodied as picture is supplied from foreign radiation sources 612, and this radiation focuses in 617 to waveguide 618, and is distributed to from waveguide 618 grating 621 be present in cylinder 604 inner surface 601.
Fig. 6 D is the schematic diagram of embodiment 640, and the radiation being wherein used for being embodied as picture is supplied from two foreign radiation sources 612A and 612B, and focuses on 621 and 619 respectively being present on the grating 621 on cylinder 604 inner surface 601.
Fig. 7 A illustrates multiple cylinder, the schematic diagram of the such as use of two cylinders 702 and 704, such as, provides continuously and can be used to obtain such as more high-resolution multigraph patterning.
Fig. 7 B is generalized section, and the pattern 706 created by the first cylinder 702 after radiation-sensitive materials 710 imaging and development is shown.The pattern 708 changed is after radiation-sensitive materials 710 imaging and development, and the pattern 708 wherein changed creates by using the first cylinder 702 be combined with the second cylinder 704.
Fig. 8 illustrates the generalized section of deformable cylinder 800, uses the equipment 813 of supply optics transparent gas to pressurize to the inside 804 of this deformable cylinder 800.The outer surface 811 of deformable cylinder 800 can be the nano-patterning/nano-structure film 812 of applicable material, this film 812 can roll on uneven substrate 805, and the radiation being therefore derived from radiation source 802 can accurately be applied on the surface 816 of substrate 805.
Detailed description of the invention
As the foreword described in detail, it is noted that use in this description and claim singulative " ", " one ", and " being somebody's turn to do " comprises plural reference, except clearly specifying within a context.
When word " approximately " uses at this, this mean represent propose nominal value be accurate to ± 10% scope in.
Embodiments of the invention relate to method and apparatus useful in the nano-patterning of extensive substrate, and wherein mask is used for radiation-sensitive materials imaging.Usual rotary mask comprises cylinder.Nano-patterning technology utilizes near field photolithography, and being wherein used for the wavelength of the radiation of the radiation-sensitive layer imaging on substrate is 438nm or shorter, and is wherein used for the mask of tpo substrate patterning and substrate contact.Near field photolithography can utilize phase-shift mask, or utilizes nano particle on the surface of transparent rotating cylindrical body, or can using plasma technology, and the metal level wherein on rotating cylindrical body surface comprises nano-pore.The detailed description provided below can have been read the sample of the possibility that those skilled in the art disclosed in this understand.
Although the rotary mask being used for generating nano-pattern in radiation sensitive material layer can have configuration useful arbitrarily, and these useful configurations many are described below, but the cylinder of hollow is advantageous particularly in the substrate manufacturing picture with minimum maintenance cost.Figure 1A illustrates the profile of an embodiment of equipment 100 useful in backing material large area pattern, and wherein radioparent cylinder 106 has the inside 104 of hollow, and radiation source 102 is present in this inside 104.In this embodiment, the outer surface 111 of cylinder 106 is by special surface embossment 112 patterning.Cylinder 106 rolls on the radiation-sensitive materials 108 covering substrate 110.Figure 1B illustrates the top view of graphic equipment and substrate in Figure 1A, and wherein radiation-sensitive materials 108 has been through the radiation (not shown) imaging 109 of surface relief 112.Cylinder rotates with the direction shown in arrow 118, and what be derived from radiation source 102 is radiated through the nano-pattern 112 be present on the outer surface 103 of rotating cylindrical body 106, thus by the radiation-sensitive layer (not shown) imaging on substrate 108, in this radiation-sensitive layer, be provided as the pattern 109 of picture.Radiation-sensitive layer develops substantially, thus is provided in the nanostructured on the surface of substrate 108.In fig. ib, rotatable cylinder 106 and substrate 120 are illustrated drive toward each other.In another embodiment, substrate 120 can maintain the dynamic Contact with rotatable cylinder 106, and with towards or direction away from the contact surface of rotatable cylinder 106 move, thus provide mobile to other static removable cylinder 106.In another embodiment, when substrate is static, rotatable cylinder 106 can rotate on substrate 120.
Special surface embossment 112 may be etched in the outer surface of transparent rotating cylindrical body 106.In alternative embodiments, special surface embossment 112 can be present in adhere to transparent rotating cylindrical body 106 outer surface polymeric material film on.By being deposited to by polymeric material, mould (motherboard) is upper to be produced this polymeric material film.This motherboard, the motherboard such as created on a silicon substrate, uses pattern electron-beam direct writing usually in the photoresist be present on silicon substrate.This pattern etches in silicon substrate subsequently.Then the pattern on silicon motherboard mould copies in precipitation polymeric material on the mold surface.This polymeric material is preferably conformable material, and this conformable material shows enough hardness, thus durable when being used as relative with substrate contact mask, but this conformable material also can produce and contacts with the outstanding of radiation-sensitive materials on the surface of a substrate.The example that this conformable material is typically used as transfer masking material is PDMS, and this PDMS can cast on motherboard die surface, uses UV radiation curing, and peels off from mould, thus produces copying remarkably of die surface.
Fig. 2 illustrates section Figure 200 of another embodiment of equipment useful in backing material large area pattern.In fig. 2, substrate is film 208, and when film 208 moves to volume 213 from volume 211, the pattern on this film 208 is passed in the radiant image of the surface relief 212 on first (transparent) cylinder 206.Second cylinder 215 provides on the back 209 of film 208, thus the contact between controlling diaphragm 208 and the first cylinder 206.Radiation source 202 is present in the hollow space 204 inside transparent cylinder 206, and this radiation source 202 can be to provide the mercury vapor lamp or other radiation source that wavelength is the radiation of 365nm or shorter.Surface relief 212 can be such as phase-shift mask, and wherein this mask comprises the Difraction surface with multiple depression and protrusion, as described in the background art.The surface contact of this protrusion and positive photoresist (radiation-sensitive materials), and this surface is exposed to electromagnetic radiation by phase mask.Due to the radiation through the depression contrary with protrusion, phase shift completes substantially.Therefore the boundary of the minimum in electromagnetic radiation intensity between depression and protrusion produces.Elasticity phase mask meets photoresist surface well, and succeeded by the development of photoresist, can obtain the characteristic size being less than 100nm.
Fig. 3 illustrates the profile 300 of another embodiment of equipment useful in backing material large area pattern.Substrate is the film 308 moving to volume 313 from volume 311.The top 310 and bottom 309 of film 308 all has radiation-sensitive layer (not shown).Have comprise radiation source 302 hollow 304 the first transparent cylinder 306 there is surface relief 312, this first transparent cylinder 306 is for top 310 patterning by film 308.Have comprise radiation source 332 hollow 324 the second transparent cylinder 326 there is surface relief 332, this second transparent cylinder 326 is for bottom 309 patterning by film 308.
Fig. 4 A illustrates the profile 400 of the embodiment of the transparent cylinder 406 comprising the hollow area 404 with internal source of radiation 402.Surface relief 412 is the conformal structures comprising the polymer film 415 had for the useful especially patterned surface 413 of near field photolithography.The polymeric material of patterned surface 413 needs enough hard, to make pattern contacts substrate surface thus in correct position imaging.Meanwhile, polymeric material must meet the surface of the radiation-sensitive materials (not shown) be imaged.
Fig. 4 B illustrates the amplification on surface 413, and this surface 413 is the surface relief polymer architectures 413 on polymer-based material 415.In figure 4b, polymer-based material 415 can be the polymeric material identical with patterned surface material 413, can be maybe the polymeric material different from patterned surface material 413.Transparent conformable material, such as silicones (silicone) or PDMS, such as, can bond material harder transparent covering layer be used as polymer film 415, this material such as has the PDMS of different mixing ratio of components, or such as polymetylmethacrylate.This provide patterned surface 413, this patterned surface 413 helps the distortion avoiding the feature contacted with the position in the sensitive surface of substrate (not shown), although polymeric base material provides the uniformity with this substrate usually simultaneously.
Fig. 5 A illustrates the profile 500 of the transparent cylinder 506 with the hollow area 504 comprising radiation source 502, wherein the alternative embodiment of surperficial 511 presentation surface embossments 512.Fig. 5 B illustrates the amplification of surface relief 512, and this surface relief 512 is the thin metal layers 514 by a series of nano-pore 513 patterning, and wherein metal level is present on the outer surface 511 of the transparent cylinder 506 of hollow.This metal level can be the patterned layer of the outer surface adhering to transparent cylinder 506.In alternative embodiments, by evaporating or sputtering or another known technology of this area, metal level is precipitable at transparent cylinder on the surface, so with laser-induced thermal etching or ablation, thus can provide the outer metallic surface 511 of patterning subsequently.Fig. 5 C illustrates the replaceable surface relief 522 that can be used on transparent cylinder 506 surface.Surface relief 522 is formed by metallic particles 526, and this metallic particles 526 can be applicable on the outer surface 511 of the transparent cylinder 506 of hollow, or can be applicable on the hyaline membrane 524 of outer surface 511 of the transparent cylinder 506 being attached to hollow.
Fig. 6 A is the schematic three dimensional views 600 of the transparent cylinder 604 with patterned surface 608.It is inner that radiation source (not shown) is present in transparent cylinder 604.Transparent cylinder 604 is used as spring to be suspended on above substrate 610 at the tensioning apparatus 602 shown in diagram 600.Mechanical engineering field professional and technical personnel can be familiar with many tensioning apparatus, and this many tensioning apparatus can be used to the appropriate amount of the contact obtained between the outer surface 608 and the surface of substrate 610 of transparent cylinder 604.In the embodiment method using the equipment shown in Fig. 6 A, this equipment is used for the imaging on substrate 610 of radiation-sensitive materials (not shown), and wherein substrate 610 is supply and the polymer film regained in this kind of volume to volume system shown in figure 2.Transparent cylinder 604 declines (or polymeric film substrate rising) towards polymeric film substrate, contacts until produce with radiation-sensitive materials.Normally elastomeric polymer film creates the Van-der-Walls power connect with radiation-sensitive materials.Then transparent cylinder 604 can rise the position of keeping in touch between (or polymer film decline) to the surface 608 and radiation-sensitive materials surface of transparent cylinder 604, but the tension force between two surfaces is arranged on power minimum on surface 608.This makes on the surface 608 of transparent cylinder 604, use very meticulous nano-patterning feature to become possibility.When substrate 610 starts mobile, transparent cylinder 604 also can move, and forces transparent cylinder 604 to rotate, and keeps the dynamic Contact between radiation-sensitive materials and lower polymer film substrate 610.In dynamic exposure whenever, the contact between cylinder and photosensitive layer is restricted to a narrow line.Due to the elastic membrane such as on cylindrical outer surface and the strong Van-derWaals power between radiosensitive (photosensitive) layer on substrate, in whole technique, contact remains even, and keeps uniform contact along whole width of mask (length) on a cylinder surface.Do not provide between cylinder contact surface and photosensitive layer in Van-derWaals power in the example of enough strong adhesion, can use actuating (rotation) cylinder, this actuating cylinder uses the stepper motor synchronous with the translation of substrate.This provide the free slippage exposure technology of polymeric cylinder surfacing or other periphery material, this periphery material does not provide the strong adhesion about substrate.
Fig. 6 B is the schematic diagram of embodiment 620, and the radiation being wherein used for being embodied as picture is supplied from the radiation source 612 in cylinder 604 outside, and radiation is inner distribution 615 and 616 inside the hollow space of cylinder 604.This radiation can be directed toward the radiation-sensitive materials surface (not shown) of various lens, speculum or its substrate 608 combined, through transparent cylinder 604, through patterned mask surface 608.
Fig. 6 C is the schematic diagram of embodiment 630, and the radiation being wherein used for realizing radiation-sensitive materials imaging is supplied from the position in transparent cylinder 604 outside.Foreign radiation sources 612 focuses in 617 to waveguide 618, and is distributed to from waveguide 618 grating 620 be present in cylinder 604 inner surface 601.
Fig. 6 D is the schematic diagram of embodiment 640, and the radiation being wherein used for being embodied as picture is supplied from two foreign radiation sources 612A and 612B, and focuses on 621 and 619 respectively being present in the grating 620 on cylinder 604 inner surface 601.
Fig. 7 A illustrates multiple cylinder, the schematic diagram 700 of the such as use of two cylinders 702 and 704, such as, provides continuously and can be used for obtaining such as more high-resolution multigraph patterning.The data being derived from the interferometer (not shown) be combined with computerization control system (not shown) such as can be used to control the region of interest of cylinder 702 and 704.
Fig. 7 B is generalized section 720, and the pattern 706 created by the first cylinder 702 after radiation-sensitive materials 710 imaging and development is shown.The pattern 708 changed is after radiation-sensitive materials 710 imaging and development, and the pattern 708 wherein changed creates by using the first cylinder 702 be combined with the second cylinder 704.
Fig. 8 illustrates the generalized section of deformable cylinder 800, and use supply optics transparent gas, the equipment 813 of such as nitrogen pressurizes to the inside 804 of this deformable cylinder 800.The outer surface 811 of deformable cylinder 800 can be the nano-patterning/nano-structure film 812 of applicable material, this film 812 can roll on uneven substrate 805, and the radiation being therefore derived from radiation source 802 can accurately be applied on the surface 816 of substrate 805.
In another embodiment, refractive index is present on substrate surface higher than the liquid of the refractive index that can use between periphery and radiosensitive (such as, photosensitive) material.Such as, water can be used.Which enhance the contrast of pattern characteristics in the photo layer.
Although for multiple embodiments above describe the present invention in detail, the various changes in category of the present invention and spirit have been obvious concerning the art professional and technical personnel.Therefore, category of the present invention should be defined by claim.

Claims (31)

1. a method for near-field nanometer photoetching, comprises:
A) provide substrate, described substrate has the solid state radiation sensitive layer on described substrate surface;
B) provide rotatable mask, described rotatable mask has the nano-pattern on the outer surface of described rotatable mask, and wherein said nano-pattern is formed by conformable material, its conformal described solid state radiation sensitive layer on described substrate surface;
C) described nano-pattern is made to contact with the described solid state radiation sensitive layer on described substrate surface;
When d) making described rotatable mask rotate on described radiation-sensitive layer, by described nano-pattern by radiation profiles, in described solid state radiation sensitive layer, create image thus.
2. method according to claim 1, the scope of the characteristic size of the feature of wherein said image is from being less than 1 μm down to about 1nm.
3. method according to claim 2, the scope of wherein said characteristic size is from about 100nm down to about 10nm.
4. method according to claim 1, the wavelength of wherein said radiation is 436nm or less.
5. method according to claim 1, wherein said nano-pattern is the polymeric material of polymeric material or the nanostructured be shaped.
6. method according to claim 4, wherein said rotatable mask is the phase shifting mask causing radiation to form interference figure in described radiation-sensitive layer.
7. method according to claim 4, wherein said mask adopts surface plasma bulk properties.
8. method according to claim 1, wherein said rotatable mask is cylinder.
9. method according to claim 8, wherein said cylinder has flexible wall, thus described cylindrical can contact described substrate surface time be out of shape.
10. method according to claim 9, wherein optical clear gas is used to be full of described cylinder.
11. methods according to claim 4, wherein said rotatable mask is transparent cylinder, and radiation can from described cylindrical interior location transmission thus.
12. methods according to claim 11, wherein said mask is the phase shifting mask be present in as embossment on the surface of described transparent cylinder.
13. methods according to claim 11, wherein said mask is the phase shifting mask be present on the layer of described cylindrical surface application.
14. methods according to claim 13, wherein at least one nano thin-film is applied to described cylindrical outer surface, thus the characteristic size of imaging in described radiation-sensitive layer shows the characteristic size of regulation more accurately.
15. methods according to claim 8, wherein during the distribution of the radiation from described cylindrical described contact surface, described substrate moves towards or away from the direction of the contact surface of described rotatable cylinder.
16. methods according to claim 8, wherein said cylinder rotates over the substrate when described substrate is static.
17. methods according to claim 1, wherein multiple spinning mask contacts with radiation-sensitive layer.
18. methods according to claim 1, wherein said rotatable mask and described substrate surface use stepper motor and motorization substrate translation machinery independently to move, and the movement of wherein said rotatable mask and described substrate is synchronous mutually, realizes exposing without slide lines of described radiation-sensitive layer thus.
19. methods according to claim 1, wherein liquid is supplied to the interface between described rotatable mask and described substrate surface.
20. methods according to claim 1, comprise the contact between surface and the surface of described radiation-sensitive materials maintaining described rotatable mask further, so that the tension force between these two surfaces makes the power on the surface of described mask minimum.
21. 1 kinds of equipment performing photoetching, comprise:
A) rotatable mask, described rotatable mask has nano-pattern on its outer surface, and wherein said nano-pattern is formed by conformable material; And
B) radiation source; when described nano-pattern contacts with the solid state radiation sensitive layer of material; described radiation source is by described nano-pattern supply radiation; wherein said rotatable mask comprises rigid cylinder; wherein said conformable material is the transparent membrane on the outer surface of described rigid cylinder; and wherein said rotatable mask also comprises the metal level on described transparent membrane; described rotatable mask is configured to adopt the radiation using surface plasma body technique to generate, thus produces photochemistry or the optical physics change of described radiation-sensitive layer.
22. equipment according to claim 21, wherein said rotatable mask is phase shifting mask.
23. equipment according to claim 22, the surface of wherein said mask comprises the metal level comprising nano-pore.
24. according to the equipment in claim 21 to claim 23 described in any one, and wherein said rotatable mask is cylinder.
25. equipment according to claim 24, wherein said cylinder is flexible cylindrical body.
26. equipment according to claim 25, wherein said flexible cylindrical body is full of optical clear gas.
27. equipment according to claim 24, wherein multiple cylinder is present in arrangement, and therefore described multiple cylinder crosses substrate successively.
, wherein there is multiple cylinder in 28. equipment according to claim 24, and wherein cylinder is present in by the top of the substrate of described equipment imaging and bottom.
29. equipment according to claim 28, at least one cylinder wherein transmitting image-forming radiation is present in by the top of the substrate of described equipment imaging and bottom.
30. equipment according to claim 21, wherein said rotatable mask is suspended on above described substrate by described tensioning apparatus.
31. equipment according to claim 21, comprise further:
Strainer, it is configured to maintain the contact between the surface of described rotatable mask and the surface of described radiation-sensitive materials, so that the tension force between these two surfaces makes the power on the surface of described mask minimum.
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